JP2000229932A - Ab2 polymerizable compound having active methylene type oxyalkylene residue and polyalkylene oxide polybranched polymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject new compound which has an active methylene type oxyalkylene oligomer residue and is useful as a raw material for polybranched polymers useful as polymer electrolytes, solid battery materials, thermally elastic polymer materials, water-absorbing polymers, and the like. SOLUTION: A compound of formula I [R is a 2-3C alkylene; (n) is 2-12; and X is a halogen]. For example, p-(2-bromoethoxy(ethoxy))-phenylacetonitrile. The compound of formula I, for example, a compound of formula II (R is CH2CH2), is obtained by dissolving hydroxyphenylacetonitrile and hydroxyethylpoly(oxyethyl) chloride in a polar solvent, adding anhydrous potassium carbonate to the mixture solution, heating and stirring the mixture, distilling away the solvent after the reaction is finished, adding a hydrophobic organic solvent and distilled water to the concentrated product, subjecting the mixture to fractionation extraction, filtration, concentration and separation purification treatments, further adding triphenyl phosphine and carbon tetrahalide, stirring the mixture, distilling away the solvent under vacuum, adding methylene chloride to the residue, and subjecting the mixture to a separation treatment, a purification treatment, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an active methylene type AB
_{(2) With} regard to polybranched polyalkylene oxides from polymerizable compounds and their monomers, more specifically, a polymer electrolyte having a skeleton and a functional group of polyethylene oxide, polypropylene oxide or polyisopropylene oxide in a unique branched structure, The present invention relates to a multi-branched polymer useful as a solid battery material, a heat-stretchable polymer material, and a water-absorbing polymer.

[0002]

2. Description of the Related Art Polyethylene oxide (hereinafter abbreviated as PEO) or polypropylene oxide (hereinafter abbreviated as PP).
O is abbreviated. ) Are industrially very useful polymers whose chemical multidimensional structure has been e.g.
By constructing a block polymer or a graft polymer of PPO, its function and properties can be controlled. Research on the development of multi-dimensional PEOs from known PEO application developments is also being actively pursued. Most of conventional PEOs are linear, and even in the production of graft polymers, basically, only materials having a structure in which linear oxyethylene is bonded to the main chain of the linear main polymer in a dangling manner. Have been.

[0003] Polymer Engineering and
Science (Polym. Eng. Sci.) ", Volume 20, 478
Page (1980) discloses that a PEO polymer having a branched structure can be obtained by utilizing the stable radical-forming ability of linear PEO under deoxygenation conditions. PCT Application International Publication Number WO97 /
In the specification of No. 2775, methylene hydrogen of PEO is extracted under light irradiation conditions or in the presence of a radical initiator, and P
It is disclosed that a polymer having a branched structure can be obtained by forming a macro radical of EO and reacting the radical.

On the other hand, "Electrochim. Acta." Vol. 43, p. 1177 (19)
1998) discloses a synthesis method for obtaining a PEO polymer having a multi-branch structure from a macromonomer having a PEO branch structure in a side chain.

[0005]

However, in the above-mentioned prior art, the polymer skeleton is highly branched like a tree, and a block segment having an oxyethylene residue in the branched structure is mainly used. It was not possible to produce a PEO-type polymer having a structure in which the chains were randomly linked without distinction between chains and side chains.

An object of the present invention is to provide, between the A and B ₂ reactive groups of the active methylene compound AB ₂ type monomer (phenylacetonitrile compound having a proton B ₂ halogens A and active methylene), multiple oxy A compound having an oligomer residue of ethylene, oxypropylene or oxyisopropylene is provided, and the active methylene AB
Using a polycondensation method involving _two monomers, a large number of oxyethylene, oxypropylene or oxyisopropylene oligomer residues in the polymer skeleton of a multi-branched structure formed from AB ₂ monomers, without distinguishing between main and side chains, An object of the present invention is to provide hyperbranched polyethylene oxide, polypropylene oxide and polyisopropylene oxide polymers which are randomly spread by carbon-carbon bonds.

[0007]

According to the present invention, there is provided a compound represented by the general formula (I):

[0008]

Embedded image

Wherein R represents a straight-chain alkylene or branched alkylene having 2 to 3 carbon atoms, and n represents 2 to 12 carbon atoms.
And X represents a halogen atom. The present invention provides an active methylene (CH ₂ CN) type AB ₂ polymerizable compound represented by the formula:

In order to solve the above problems, the present invention provides a compound represented by the general formula (V):

[0011]

Embedded image

(Wherein, R represents a linear alkylene or branched alkylene having 2 to 3 carbon atoms, and n represents 2 to 12 carbon atoms.)
And X represents a halogen atom. The present invention provides a multibranched polyalkylene oxide polymer represented by the formula:

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The compound represented by the general formula (I) of the present invention can be produced, for example, according to the following production method.

(1) In the general formula (I), -R- is-
General formula (II) which is CH ₂ CH ₂ —

[0015]

Embedded image

(Wherein n represents an integer of 2 to 12;
Represents a halogen atom. Active methylene (CH ₂ CN) type AB ₂ polymerizable compound represented by the formula:

To a mixed solution of hydroxyphenylacetonitrile and hydroxyethyl poly (oxyethylene) chloride dissolved in a polar solvent, anhydrous potassium carbonate is added. The mixture is heated to a temperature of at least 80 ° C. and stirred for at least 10 hours. After completion of the reaction, the solvent in the reaction mixture is distilled off under reduced pressure. A hydrophobic organic solvent is added to the concentrate, and distilled water is further added to the organic solution to carry out liquid separation extraction.
Anhydrous magnesium sulfate is added to the obtained organic layer solution and dried, followed by suction filtration. The filtrate is concentrated and then separated and purified using silica gel chromatography using ethyl acetate as an eluent. The solution after the separation is concentrated under reduced pressure, and further dried under vacuum, whereby the compound (precursor) in which X is OH in the general formula (II) is 80%.
The above yield can be obtained.

The precursor obtained in the above reaction is dissolved in dehydrated tetrahydrofuran, and triphenylphosphine and carbon tetrahalide (for example, carbon tetrachloride,
(Carbon tetrabromide or carbon tetraiodide), and the mixture is stirred at room temperature for 1 hour or more. After completion of the reaction, the solvent was distilled off under reduced pressure,
An appropriate amount of methylene chloride is added to the residue. The eluate was recovered from this solution using silica gel chromatography,
Concentrate under reduced pressure. Further, by drying the obtained product under vacuum, the active methylene type AB ₂ polymerizable compound represented by the general formula (II) wherein X is Cl, Br or I can be obtained in a yield of 90% or more. Can be obtained at

As the compound represented by the general formula (II) thus obtained, the oxygen atom of the-(OCH ₂ CH ₂ ) _n -group is bonded to the o-, m- or p-position of the benzene ring. Can be produced, but those having an oxygen atom bonded to the p-position are preferred. In addition, it is possible to produce a compound of the formula-(OCH ₂ CH ₂ ) _n-wherein n is an integer of 2 to 12, but n is preferably 4 to 10, more preferably 6 to 8. Is particularly preferred. Further, compounds in which X in the formula is represented by Cl, Br or I can be produced, and compounds in which X is Br are particularly preferred.

The hydroxyphenylacetonitrile compounds used in the above reaction include, for example, 2-hydroxyphenylacetonitrile, 3-hydroxyphenylacetonitrile, 4-hydroxyphenylacetonitrile and the like.

The polyoxyethylene compounds used in the above reaction include, for example, hydroxyethyloxyethyl chloride, hydroxyethyldi (oxyethylene) chloride, hydroxyethyltri (oxyethylene) chloride, hydroxyethyltetra (oxyethylene) Chloride, hydroxyethyl penta (oxyethylene) chloride, hydroxyethyl hexa (oxyethylene) chloride, hydroxyethyl hepta (oxyethylene) chloride, hydroxyethyl octa (oxyethylene) chloride, hydroxyethyl nona (oxyethylene) chloride, hydroxyethyl Deca (oxyethylene) chloride, hydroxyethylundeca (oxyethylene) chloride, and the like.

The polar solvent used in the above reaction can be used without any particular limitation as long as it is a common polar organic solvent, and among them, N, N-dimethylformamide is particularly preferred.

(2) In the general formula (I), -R- is-
General formula (III) which is CH ₂ CH ₂ CH ₂ —

[0024]

Embedded image

(Wherein n represents an integer of 2 to 12;
Represents a halogen atom. Active methylene (CH ₂ CN) type AB ₂ polymerizable compound represented by the formula:

In the production method of the above (1), except that hydroxypropyl poly (oxypropylene) chloride is used instead of hydroxyethyl poly (oxyethylene) chloride, the same as the production method of the above (1), In the general formula (III), 90% of the active methylene type AB ₂ polymerizable compound represented by X represents Cl, Br or I
The above yield can be obtained.

The compound represented by the general formula (III) thus obtained includes a compound in which the oxygen atom of the-(OCH ₂ CH ₂ ) _n -group is bonded to the o-, m- or p-position of the benzene ring. Can be produced, but those having an oxygen atom bonded to the p-position are preferred. Further, in the formula _{- (OCH 2 CH 2) n} - is n radicals can be produced which is an integer of up to 2 to 12, n is 4 to 10
Are preferred, and those of 6 to 8 are particularly preferred. Further, compounds in which X in the formula is represented by Cl, Br or I can be produced, and compounds in which X is Br are particularly preferred.

The polyoxypropylene compounds used in the above reaction include, for example, hydroxypropyloxypropyl chloride, hydroxypropyldi (oxypropylene) chloride, hydroxypropyltri (oxypropylene) chloride, hydroxypropyltetra (oxypropylene) chloride, Hydroxypropyl penta (oxypropylene) chloride, hydroxypropyl hexa (oxypropylene) chloride, hydroxypropyl hepta (oxypropylene) chloride, hydroxypropyl octa (oxypropylene) chloride, hydroxypropyl nona (oxypropylene) chloride,
Hydroxypropyldeca (oxypropylene) chloride, hydroxypropylundeca (oxypropylene)
Chloride and the like.

(3) In the general formula (I), -R- is-
General formula (IV) which is CH ₂ CH (CH ₃ ) —

[0030]

Embedded image

(Wherein, n represents an integer of 2 to 12;
Represents a halogen atom. Active methylene (CH ₂ CN) type AB ₂ polymerizable compound represented by the formula:

In the above method (1), except that hydroxyisopropyl poly (oxyisopropylene) chloride is used instead of hydroxyethyl poly (oxyethylene) chloride, the same method as in the above method (1) is used. An active methylene type AB ₂ polymerizable compound represented by formula (IV) wherein X is Cl, Br or I
It can be obtained with a yield of 0% or more.

As the compound represented by the general formula (IV) thus obtained, the oxygen atom of the-(OCH ₂ CH ₂ ) _n -group is bonded to the o-, m- or p-position of the benzene ring. Can be produced, but those having an oxygen atom bonded to the p-position are preferred. In addition, it is possible to produce a compound of the formula-(OCH ₂ CH ₂ ) _n-wherein n is an integer of 2 to 12, but n is preferably 4 to 10, more preferably 6 to 8. Is particularly preferred. Further, compounds in which X in the formula is represented by Cl, Br or I can be produced, and compounds in which X is Br are particularly preferred.

Examples of the polyoxypropylene compound used in the above reaction include hydroxyisopropyloxyisopropyl chloride, hydroxyisopropyl di (oxyisopropylene) chloride, hydroxyisopropyl tri (oxyisopropylene) chloride, and hydroxyisopropyl tetra (oxyisopropylene). )
Chloride, hydroxyisopropylpenta (oxyisopropylene) chloride, hydroxyisopropylhexa (oxyisopropylene) chloride, hydroxyisopropylhepta (oxyisopropylene) chloride, hydroxyisopropylocta (oxyisopropylene)
Chloride, hydroxyisopropyl nona (oxyisopropylene) chloride, hydroxyisopropyl deca (oxyisopropylene) chloride, hydroxyisopropyl undeca (oxyisopropylene) chloride, and the like.

The polybranched polyalkylene oxide polymer represented by the general formula (V) can be produced, for example, according to the following production method.

(4) In the general formula (V), -R- is-
General formula (VI) which is CH ₂ CH ₂ —

[0037]

Embedded image

(Wherein, n represents an integer of 2 to 12;
Represents a halogen atom. )) Is a multi-branched polyethylene oxide polymer

An aqueous solution of sodium hydroxide is added all at once to a polar solvent of the active methylene type AB ₂ monomer represented by the general formula (II), and the mixture is reacted at room temperature for 30 minutes or more with stirring. Add distilled water. Next, an aqueous solution of hydrochloric acid is added dropwise to neutralize the aqueous solution of the reaction system to precipitate the product. The precipitated reaction product is filtered off and washed with distilled water. After the reaction product has been dried at room temperature, it is dissolved in tetrahydrofuran, the solution is poured into petroleum ether and the reaction product is reprecipitated. The precipitated reaction product is separated by filtration, dried at room temperature and further dried under vacuum for 24 hours to obtain a multibranched polyethylene oxide polymer represented by the general formula (VI).
It can be obtained with a yield of 5% or more.

In the thus obtained hyperbranched polyethylene oxide polymer represented by the general formula (VI), the oxygen atom of the — (OCH ₂ CH ₂ ) _n — group in the formula is represented by - it can be produced those attached to m- or p- position, in the formula - (OCH ₂ CH _{2) n}
Those in which the oxygen atom of the group is bonded to the p-position of the benzene ring are preferred.

The general formula (II) used in this polymerization reaction
Polymethylene type active methylene AB represented by
₂ monomers, of the formula _{- (OCH 2 CH 2) n} - in, n represents preferably has up to 2 to 12, n is 6-8
Are particularly preferred. Further, in formula (II),-(O
CH ₂ CH ₂ ) _n — wherein the oxygen atom is bonded to the o-, m- or p-position of the benzene ring,
In the formula _{- (OCH 2 CH 2) n} - oxygen atom of the group is, those bonded to p- position of the benzene ring are preferred.

Furthermore, the general formula (II) used in this polymerization reaction
Polymethylene type active methylene AB represented by
_{The two} monomers are preferably those in which X in the formula is represented by Cl, Br or I, and those in which X is Br are particularly preferred.

The polar solvent used in this polymerization reaction may be any of commonly used polar organic solvents, and among them, a polar solvent such as dimethyl sulfoside, N, N-dimethylformamide and acetonitrile is particularly preferable.

The aqueous alkali solution used for this polymerization reaction is
A strong alkaline aqueous solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution is desirable. The concentration of the alkaline aqueous solution is preferably in the range of 20 to 50%, and particularly preferably 40%. The amount of the aqueous alkali solution used is sufficient to be 4 times the molar number of the phenylacetonitrile, but in order to allow the polymerization reaction to proceed smoothly, the amount of the alkali used should be set to 10 times the molar amount or more. desirable.

As the alkali used in the aqueous alkali solution, an organic alkali compound other than the above-mentioned inorganic alkalis can be used. Examples of such organic alkali compounds include, for example, onium hydroxides such as 1,3-diaza [4.5] bicycloundecene, p-dimethylaminopyridine, tetrabutylammonium hydroxide, and triphenylbedylphosphonium hydroxide. And the like.

The temperature of the polymerization reaction is preferably in the range of room temperature to 60 ° C., particularly preferably in the range of room temperature to 40 ° C.
A 30 ° C. range is more preferred.

The polymerization reaction time in the range of 0.5 to 6 hours is sufficient, but it is desirable to set the reaction time according to the concentration of the aqueous alkali solution. For example, when a 40% alkaline aqueous solution is used, the reaction time after the addition of the alkaline aqueous solution is preferably set to one hour.

The alkaline reaction mixture containing the reaction product dissolves easily in water. A hydrochloric acid aqueous solution is added to such an aqueous solution, and the pH value of the mixed solution is made neutral to weakly acidic, whereby the reaction product precipitates. In this precipitation process, the concentration of the aqueous hydrochloric acid solution used is preferably in the range of 5 to 10%. The obtained precipitate of the reaction product is easily dissolved in the polar organic solvent. Examples of the non-solvent in which the reaction product becomes insoluble include diethyl ether, hexane, petroleum ether and the like. It is desirable to purify the obtained reaction purified product by reprecipitation. Preferred good solvents used in the reprecipitation process include tetrahydrofuran, and preferred non-solvents include petroleum ether.

The thus obtained hyperbranched polyethylene oxide polymer represented by the general formula (VI) has chlorine, bromine or iodine bonded to the facal terminal, but is not limited thereto. , Hydroxyl,
It may be an amino group or an ether group.

(5) In the general formula (V), -R- is-
Formula (VII) which is CH ₂ CH ₂ CH ₂ —

[0051]

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(Wherein, n represents an integer of 2 to 12;
Represents a halogen atom. )) Polybranched polypropylene oxide polymers represented by

[0053] (4) In the manufacturing method of the general formula in place of the active methylene type AB ₂ monomers represented by (II), Formula active methylene type represented by (III) AB ₂
Except for using a monomer, a multibranched polypropylene oxide polymer represented by the general formula (VII) can be obtained in a yield of 85% or more in the same manner as in the production method of the above (4).

In the thus obtained hyperbranched polypropylene oxide polymer represented by the general formula (VII), the oxygen atom of the — (OCH ₂ CH ₂ CH ₂ ) _n — group in the formula has a benzene ring. Bruno o-, can be produced those attached to m- or p- position, in the formula - (OCH ₂
It is preferable that the oxygen atom of the CH ₂ CH ₂ ) _n group be bonded to the p-position of the benzene ring.

The general formula (II) used in this polymerization reaction
Polyoxypropylenes active methylene type AB ₂ monomer represented by I) are of the formula _{- (OCH 2 CH 2 CH 2} ) n
In-, n is preferably from 2 to 12, particularly preferably from 6 to 8. In the formula (III),-(OCH ₂ CH ₂ CH ₂ ) _n -has an oxygen atom bonded to the o-, m- or p-position of the benzene ring. It is preferable that the oxygen atom of the — (OCH ₂ CH ₂ CH ₂ ) _n — group is bonded to the p-position of the benzene ring.

Furthermore, the general formula (II) used in this polymerization reaction
The active methylene type AB ₂ monomer represented by the formula (I) is preferably a compound wherein X in the formula is Cl, Br or I, and particularly preferably a compound wherein X is Br.

The thus obtained hyperbranched polypropylene oxide polymer represented by the general formula (VII) has chlorine, bromine or iodine bonded to the facal terminal, but is not limited thereto. , A hydroxyl group, an amino group or an ether group.

(6) In the general formula (V), -R- is-
General formula (VIII) which is CH ₂ CH (CH ₃ ) —

[0059]

Embedded image

(Wherein, n represents an integer of 2 to 12;
Represents a halogen atom. The polybranched polyisopropylene oxide polymers represented by)

[0061] (4) In the manufacturing method of the general formula in place of the active methylene type AB ₂ monomers represented by (II), Formula active methylene type represented by (IV) AB ₂
Except that a monomer is used, a multibranched polyisopropylene oxide polymer represented by the general formula (VIII) can be obtained in a yield of 85% or more in the same manner as in the production method of the above (4).

The hyperbranched polyisopropylene oxide polymer represented by the general formula (VIII) thus obtained includes an oxygen atom of a-(OCH ₂ CH (CH ₃ )) _n -group in the formula. , A compound bonded to the o-, m- or p-position of the benzene ring can be produced,
It is preferred that the oxygen atom of the (OCH ₂ CH (CH ₃ )) _n -group be bonded to the p-position of the benzene ring.

The general formula (IV) used in this polymerization reaction
Polyoxypropylene isopropylene such active methylene-type AB ₂ monomer represented in the in the formula - (OCH ₂ CH (C
H ₃ )) In _n −, n is preferably from 2 to 12, and particularly preferably from 6 to 8. Further, in-(OCH ₂ CH (CH ₃ )) _n -in the general formula (III),
The oxygen atom is bonded to the o-, m-, or p-position of the benzene ring. In the formula,-(OCH ₂ CH (C
H ₃ )) Those in which the oxygen atom of the _n -group is bonded to the p-position of the benzene ring are preferred.

Further, the general formula (IV) used in this polymerization reaction
In the polyoxyisopropylene type active methylene type AB ₂ monomer represented by the formula, X in the formula is preferably represented by Cl, Br or I, and X is preferably Br.

The thus obtained hyperbranched polyisopropylene oxide polymer represented by the general formula (VIII) has chlorine, bromine or iodine bonded to the facal terminal, but is not necessarily limited thereto. Instead, it may be a hydroxyl group, an amino group or an ether group.

[0066]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the scope of these Examples.

<Example 1> [p- (2-bromoethoxy (ethoxy))-phenylacetonitrile (N2E-
Synthesis of Br)] (Synthesis of Precursor) Capacity 1000 ml with Magnetic Stirrer
79.83 g of 4-hydroxyphenylacetonitrile, 2-chloroethoxyethanol 1
11.63 g, 125 g of anhydrous potassium carbonate and N, N-
500 ml of dimethylformamide were added sequentially. The mixture was heated to 80 ° C. and stirring was continued at the same temperature for 12 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, and 500 ml of methylene chloride was added to the residue. In addition to this mixture,
500 ml of distilled water was added, and the reaction product was extracted with a separating funnel. The remaining aqueous layer was further extracted with 300 ml of methylene chloride. The methylene chloride layer was recovered, 40 g of anhydrous magnesium sulfate was added to the solution, and the solution was dried with stirring. After the solution was filtered and concentrated, the reaction product was isolated and purified by silica gel chromatography using ethyl acetate as an eluent. The resulting reaction product is placed under vacuum for 24 hours.
After drying for an hour, 113.22 g (yield: 85%) of a precursor compound (hereinafter abbreviated as N2E-OH) was obtained.

NE2-OH obtained above was identified as follows. ¹ H NMR (CDCl ₃ , internal standard: TMS): δ: 2.5 (1H, OH), 3.64-3.66 (m,
2H, CH ₂ OH), 3.67 (s, 2H, CH ₂ C)
N), 3.72~3.76 (t, 2H , CH 2 O),
_{3.83~3.86 (t, 2H, CH 2} O), 4.10
_{~4.13 (t, 2H, CH 2} OPh), 6.88~
6.93 (d, 2H, PhH), 7.12-7.23
(D, 2H, PhH)

¹³ C NMR (CDCl ₃ , internal standard: TMS): δ: 22.6, 61.5, 67.3, 69.3, 72.
5, 115.0, 118.0, 122.0, 128.
9,158.2

HR-Mass (m / z): (C ₁₂ H ₁₅ NO ₃ ) measured value: 221.1073 calculated value: 221.1051

(Synthesis of the title compound) Into a 500 ml eggplant-shaped flask equipped with a magnetic stirrer,
110.5 g of E-OH, 167.8 g of carbon tetrabromide and 30 ml of tetrahydrofuran were sequentially added, and the mixture was stirred until a transparent solution was obtained. To this solution is added triphenylphosphine 1
44.1 g was added and stirring was continued at room temperature for 2 hours. After completion of the reaction, the mixture was concentrated, and methylene chloride
1 was added. Further, the reaction product was isolated and purified using silica gel chromatography using methylene chloride as an eluent. Furthermore, the obtained product was dried under vacuum for 24 hours to obtain 124.8 g (88%) of a reaction product (NE2-Br).

NE2-Br obtained above was identified as follows: ¹ H NMR (CDCl ₃ , internal standard: TMS): δ: 3.47 to 3.52 (t, 2H, CH ₂ Br) ),
_{3.68 (s, 2H, CH 2} CN), 3.74~3.7
_{7 (t, 2H, CH 2} O), 3.84~3.88 (t,
_{2H, CH 2 O), 4.10~4.13} (t, 2H, C
_{H 2 OPh), 6.88~6.93 (d} , 2H, Ph
H), 7.12-7.23 (d, 2H, PhH)

¹³ C NMR (CDCl ₃ , internal standard: TMS): δ: 22.6, 64.7, 67.8, 69.3, 72.
5, 115.0, 118.0, 122.0, 128.
9,158.2

HR-Mass (m / z): (C ₁₂ H ₁₅ BrNO ₂ ) measured value; 286.0165 calculated value; 285.0188

<Example 2> [Synthesis of polybranched polyethylene oxide polymer (Poly-NE2)] 6.3 g of N2E-Br obtained in Example 1 was placed in a 250 ml eggplant-shaped flask equipped with a magnetic stirrer. 100 ml of dimethyl sulfoxide were added. In this mixed solution,
While stirring the mixed solution using a magnetic stirrer, 30 ml of a 50% aqueous sodium hydroxide solution was added at a time, and stirring was further continued at 30 ° C. for 1 hour. After completion of the reaction, 100 ml of distilled water was added to the reaction mixture. The reaction mixture was neutralized by dropping 10% hydrochloric acid into the mixture while stirring the mixture, and after standing for 1 hour in the neutralized state, the precipitated reaction product was suction-filtered. The filtered reaction product was washed with distilled water. The reaction product after washing was dried at room temperature, dissolved in 20 ml of tetrahydrofuran, and the solution was poured into 200 ml of petroleum ether to reprecipitate the reaction product. After suction-filtration of the reprecipitated reaction product, the product is dried under reduced pressure in a desiccator with a vacuum pump for 24 hours to obtain a multibranched polyethylene oxide polymer (hereinafter, Poly-N2E).
Is abbreviated. ) 4.1 g (92% yield).

The hyperbranched polymer obtained in Example 2 (Pol
The number average molecular weight of the compound (y-N2E) measured by GPC (gel permeation / chromatography) was 13,400, and the molecular weight distribution was 1.68.

<Example 3> [Synthesis of polybranched polyethylene oxide polymer (Poly-N3E)] In the same manner as in Example 1, except that 30 ml of 50% tetrabutylammonium chloride was used as the alkali in Example 2. And a multi-branched polymer (hereinafter referred to as Poly-
Abbreviated as N3E. ) 4.3 g (97% yield).

The hyperbranched polymer obtained in Example 3 (Pol
The number average molecular weight measured using GPC of y-N2E) was 17,500, and the molecular weight distribution was 1.77.

From the results of Embodiments 1, 2, and 3, it can be understood that the problem to be solved by the present invention can be easily realized.

[0080]

According to the present invention, the active methylene type AB ₂ polymerizable monomer and the multi-branched polyethylene oxide, polypropylene oxide and polyisopropylene oxide polymers obtained by the polymerization reaction of the monomer are impossible with conventional techniques. And a polymer having a highly branched and block segmental polyethylene oxide or polypropylene oxide skeleton. The polymer of the present invention can be applied not only to the field where conventional polyethylene oxide or polypropylene oxide is used, but also to various applications as a novel multifunctional polymer material.

Claims (14)

[Claims] 1. A compound of the general formula (I) (Wherein, R represents a linear alkylene or a branched alkylene having 2 to 3 carbon atoms, n represents an integer of 2 to 12, and X represents a halogen atom). 2. A compound of the general formula (II) (Wherein, n represents an integer of 2 to 12, and X represents a halogen atom). 3. X is Br, and-(OCH ₂ CH ₂ ) _n
The polymerizable compound according to claim 2, wherein-is bonded to the p-position of the benzene ring. 4. A compound of the general formula (III) (Wherein, n represents an integer of 2 to 12, and X represents a halogen atom). 5. X is Br, and-(OCH ₂ CH ₂ CH
₂ ) The compound according to claim 4, wherein _n- is bonded to the p-position of the benzene ring. 6. A compound of the general formula (IV) (Wherein, n represents an integer of 2 to 12, and X represents a halogen atom). 7. X is Br, and-(OCH ₂ CH (C
H _{3)) n} - is a compound of claim 6, wherein attached to p- position of the benzene ring. 8. A compound of the general formula (V) (In the formula, R represents a linear alkylene or branched alkylene having 2 to 3 carbon atoms, n represents an integer of 2 to 12, and X represents a halogen atom.) Oxide polymers. 9. A compound of the general formula (VI) (Wherein, n represents an integer of 2 to 12, and X represents a halogen atom). 10. X is Br, and-(OCH ₂ CH ₂ )
_10. The multibranched polyethylene oxide polymer according to claim 9, wherein _n- is bonded to the p-position of the benzene ring. 11. A compound of the general formula (VII) (Wherein, n represents an integer of 2 to 12, and X represents a halogen atom). 12. X is Br, and-(OCH ₂ CH ₂ C
H ₂ ) _n -is bonded to the p-position of the benzene ring.
2. The hyperbranched polypropylene oxide polymer according to 1. 13. A compound of the general formula (VIII) (In the formula, n represents an integer of 2 to 12, and X represents a halogen atom.) A polybranched polyisopropylene oxide polymer represented by the following formula: 14. X is Br, and-(OCH ₂ CH
(CH _{3)) n} - is a multi-branched poly isopropylene oxides polymer of claim 13 wherein binding to p- position of the benzene ring.